JP2006255496A - Method of manufacturing laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a laminated film having low reflectance, excellent adhesion, excellent abrasion resistance, high surface hardness and free from embrittlement and coloring. <P>SOLUTION: The method of manufacturing the laminated film is carried out by applying a coating liquid containing a sol-gel reactive silicon compound and a hollow fine particle directly or through another layer on a supporting body containing a transparent resin and drying the liquid to obtain a film on which a coating film is formed and irradiating the film with electromagnetic wave. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a laminated film that can be suitably used for display devices such as a cathode ray tube (CRT), a liquid crystal display device (LCD), and a plasma display (PDP).

In recent years, in a display device represented by a cathode ray tube, a liquid crystal display device, a plasma display, or the like, a functional film is attached to the outermost surface of a panel on which an image is displayed. This functional film has various functions such as an antistatic effect, an antireflection effect, and an antifouling effect. As an example of such a functional film, a laminated film in which a hard coat layer, a high refractive index layer, a low refractive index layer and the like are laminated on a resin base material is known.
As a method of forming a low refractive index layer of a laminated film, a method of forming a polysiloxane layer using a so-called sol-gel reaction is known. According to this, the silica fine particle-dispersed sol is hydrolytically condensed, dried, and formed into a cured film, whereby a porous body of particles can be formed and a low refractive index layer can be formed. However, the formation of the low refractive index layer by the sol-gel method has problems in adhesion and scratch resistance, and further improvement has been demanded.
Therefore, a coating liquid composition containing polysiloxane and a photoacid generator is applied as a low refractive index layer, dried, and irradiated with ultraviolet rays to actively promote the sol-gel curing reaction, adhesion, and scratch resistance. It has been proposed to improve performance. However, by promoting curing, the low refractive index layer aggregates, the refractive index becomes high, and it is difficult to make the refractive index 1.40 or less (Patent Document 1).
In another embodiment, an aqueous alkoxysilane solution prepared by hydrolyzing a silicon alkoxide containing a photoreactive group is applied onto a transparent resin substrate, the formed substrate is heated and dried, and then ultraviolet rays are applied. It has been proposed to form an organopolysiloxane layer by irradiation. However, it is difficult to make the refractive index smaller than 1.38, the antireflection property is not satisfactory, and the adhesion to the film and the scratch resistance are insufficient (Patent Document 2).

JP 2002-243905 A JP 2000-198964 A

  Accordingly, an object of the present invention is to provide a production method for obtaining a laminated film having low reflectance, good adhesion, excellent scratch resistance, high surface hardness, and no embrittlement or coloring. .

  As a result of intensive studies to achieve the above object, the present inventor has applied a coating containing a sol-gel reactive silicon compound and hollow fine particles directly or via another layer on a support containing a transparent resin. It is found that the above object can be achieved by applying a coating solution and drying to obtain a film with a coating film formed thereon, and then irradiating the film with electromagnetic waves. It came to complete.

Thus, according to the present invention,
A coating solution containing a sol-gel reactive silicon compound and hollow fine particles was applied on a support containing a transparent resin, directly or via another layer, and dried to form a coating. There is provided a method for producing a laminated film, which comprises obtaining a film and then irradiating the film with electromagnetic waves.

  According to the production method of the present invention, it is possible to obtain a laminated film having low reflectance, good adhesion, excellent scratch resistance, high surface hardness, and no embrittlement or coloring.

  In the production method of the present invention, a coating solution containing a sol-gel reactive silicon compound and hollow fine particles is applied directly or via another layer onto a support containing a transparent resin, and then dried. Thus, a film on which a film is formed is obtained, and then the film is irradiated with electromagnetic waves.

  The transparent resin used in the present invention is only required to have a thickness of 1 mm and a total light transmittance of 80% or more. Specifically, the alicyclic structure-containing polymer resin, polyester resin, cellulose resin, polycarbonate Resin, polysulfone resin, polyethersulfone resin, polystyrene resin, polyolefin resin, polyvinyl alcohol resin, polyvinyl chloride resin, polymethacrylate resin and the like. These transparent resins can be used alone or in combination of two or more.

  Among these, since it is high in strength and excellent in transparency, an alicyclic structure-containing polymer resin, a cellulose polymer resin such as cellulose diacetate, cellulose triacetate, and cellulose acetate butyrate; polyethylene terephthalate, polybutylene terephthalate, Polyester polymer resins such as polyethylene naphthalate; are preferred, and from the viewpoints of high transparency, little coloration, and light weight, alicyclic structure-containing polymer resins, triacetyl cellulose and polyethylene terephthalate are more preferred. An alicyclic structure-containing polymer resin is particularly preferred.

  The alicyclic structure-containing polymer resin has an alicyclic structure in the repeating unit of the polymer resin, and the polymer resin having an alicyclic structure in the main chain and an alicyclic structure in the side chain. Any polymer resin can be used.

  Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure, and a cycloalkane structure is preferable from the viewpoint of thermal stability. Although carbon number which comprises an alicyclic structure does not have a restriction | limiting in particular, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is 5-15 pieces. When the number of carbon atoms constituting the alicyclic structure is within this range, a support having excellent heat resistance and flexibility can be obtained.

  The proportion of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer resin may be appropriately selected according to the purpose of use, but is usually 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more. When the number of repeating units having an alicyclic structure is excessively small, the heat resistance tends to decrease. In addition, repeating units other than the repeating unit which has an alicyclic structure in an alicyclic structure containing polymer resin are suitably selected according to the intended purpose.

  Specific examples of the alicyclic structure-containing polymer resin include (i) a norbornene polymer, (ii) a monocyclic olefin polymer, (iii) a cyclic conjugated diene polymer, and (iv) a vinyl alicyclic ring. Formula hydrocarbon polymers, hydrides thereof and the like. Among these, norbornene-based polymers are preferable from the viewpoints of transparency and moldability.

  Specific examples of the norbornene-based polymer include ring-opening polymers of norbornene-based monomers, ring-opening copolymers of norbornene-based monomers and other monomers capable of ring-opening copolymerization, and those Hydrides of the above, addition polymers of norbornene monomers, addition copolymers with other monomers copolymerizable with norbornene monomers, and the like. Among these, from the viewpoint of transparency, hydrogenated ring-opening polymers of norbornene monomers and hydrogen of ring-opening copolymers of norbornene monomers and other monomers capable of ring-opening copolymerization. The compound is particularly preferred.

Examples of the norbornene-based monomer include bicyclo [2.2.1] hept-2-ene (common name: norbornene), tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene. (Common name: dicyclopentadiene), 7,8-benzotricyclo [4.3.0.1 ^2,5 ] dec-3-ene (common name: methanotetrahydrofluorene), tetracyclo [4.4.0. 1 ^2,5 . 1 ^7,10 ] dodec-3-ene (common name: tetracyclododecene), derivatives of these compounds (for example, those having a substituent in the ring), and the like. Here, examples of the substituent include an alkyl group, an alkylene group, an alkoxycarbonyl group, and a carboxyl group. In addition, these substituents may be the same or different and a plurality may be bonded to the ring. Norbornene monomers can be used alone or in combination of two or more.

  Other monomers capable of ring-opening copolymerization with norbornene monomers include, for example, monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene and derivatives thereof; cyclic conjugated dienes such as cyclohexadiene and cycloheptadiene; Derivatives thereof; and the like.

  Ring-opening polymers of norbornene monomers and ring-opening copolymers of norbornene monomers and other monomers copolymerizable therewith are polymerized in the presence of a ring-opening polymerization catalyst. Can be obtained. As the ring-opening polymerization catalyst, a commonly used known catalyst can be used.

  Other monomers that can be copolymerized with norbornene monomers include, for example, α-olefins having 2 to 20 carbon atoms such as ethylene and propylene, and derivatives thereof; cycloolefins such as cyclobutene and cyclopentene, and the like. Derivatives; non-conjugated dienes such as 1,4-hexadiene and the like. These monomers can be used alone or in combination of two or more. Among these, α-olefin is preferable, and ethylene is more preferable.

  Norbornene monomer addition polymers and addition copolymers of norbornene monomers and other monomers copolymerizable therewith are obtained by polymerizing the monomers in the presence of an addition polymerization catalyst. Obtainable. As the addition polymerization catalyst, a commonly used known catalyst can be used.

  Ring-opening polymer of norbornene monomer, ring-opening copolymer of norbornene monomer and other monomer capable of ring-opening copolymerization, addition polymer of norbornene monomer, and norbornene Addition of a known hydrogenation catalyst to the hydride of an addition polymer of a system monomer and another monomer copolymerizable therewith, preferably hydrogenates a carbon-carbon unsaturated bond by 90% or more. Can be obtained.

Examples of the monocyclic olefin-based polymer include addition polymers such as cyclohexene, cycloheptene, and cyclooctene.
Examples of the cyclic conjugated diene polymer include polymers obtained by 1,2-addition polymerization or 1,4-addition polymerization of cyclic conjugated diene monomers such as cyclopentadiene and cyclohexadiene.

  The vinyl alicyclic hydrocarbon polymer is a polymer having a repeating unit derived from vinylcycloalkane or vinylcycloalkene. Examples of the vinyl alicyclic hydrocarbon polymer include polymers of vinyl alicyclic hydrocarbon compounds such as vinylcycloalkanes such as vinylcyclohexane and vinylcycloalkenes such as vinylcyclohexene and their hydrides; styrene, α-methyl Examples thereof include hydrides of aromatic ring portions of polymers of vinyl aromatic hydrocarbon compounds such as styrene.

  The vinyl alicyclic hydrocarbon polymer includes a random copolymer, a block copolymer, and a hydride thereof of a vinyl alicyclic hydrocarbon compound and another monomer copolymerizable therewith; vinyl It may be a random copolymer of an aromatic hydrocarbon compound and another monomer copolymerizable therewith or a hydride of an aromatic ring portion of a block copolymer. Examples of the block copolymer include diblock, triblock, or more multiblock and gradient block copolymers, but are not particularly limited.

  As for the molecular weight of the transparent resin, the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography using cyclohexane (toluene when the polymer resin does not dissolve) as a solvent is usually 10,000 to 300,000, When the range is preferably 15,000 to 250,000, more preferably 20,000 to 200,000, the mechanical strength and moldability of the support are highly balanced and suitable.

  The glass transition temperature of the transparent resin may be appropriately selected according to the purpose of use, but is preferably 80 ° C. or higher, more preferably 100 to 250 ° C. A support made of a transparent resin having a glass transition temperature in such a range is excellent in durability without being deformed or stressed when used under high temperature and high humidity.

  The support used in the present invention may contain other compounding agents in addition to the transparent resin as long as the effects of the present invention are not impaired. Other compounding agents include plasticizers, antioxidants, heat stabilizers, light stabilizers, UV absorbers, antistatic agents, dispersants, chlorine scavengers, flame retardants, crystallization nucleating agents, antiblocking agents, antiblocking agents. Known compounding agents such as clouding agents, release agents, pigments, organic or inorganic fillers, neutralizers, lubricants, metal deactivators, antifouling materials, antibacterial agents and other resins, thermoplastic elastomers, etc. It is done.

The support used in the present invention is preferably obtained by molding the transparent resin into a film by a known molding method.
Examples of a method for forming the transparent resin into a film include a solution casting method and a melt extrusion method. Among these, the melt extrusion molding method is preferable because the content of volatile components in the film and the thickness unevenness can be reduced. Further, examples of the melt extrusion molding method include a method using a die such as a T die, an inflation method, and the like, but a method using a T die is preferable in terms of excellent productivity and thickness accuracy.

  When adopting a method using a T die as a method for forming a film, the melting temperature of the transparent resin in the extruder having the T die should be 80 to 180 ° C. higher than the glass transition temperature of the transparent resin. Preferably, the temperature is higher by 100 to 150 ° C. If the melting temperature in the extruder is excessively low, the fluidity of the transparent resin may be insufficient. Conversely, if the melting temperature is excessively high, the resin may be deteriorated.

  Furthermore, it is preferable to pre-dry the transparent resin to be used before forming into a film. The preliminary drying is performed using, for example, a hot air dryer or the like in the form of pellets or the like. The drying temperature is preferably 100 ° C. or more, and the drying time is preferably 2 hours or more. By performing preliminary drying, the amount of volatile components in the film can be reduced, and bubbles can be prevented from being generated in the transparent resin film.

  Moreover, as a support body, what gave the surface modification process to the single side | surface or both surfaces can be used. By performing the surface modification treatment, adhesion to the low refractive index layer and other layers described later can be improved. Examples of the surface modification treatment include energy beam irradiation treatment and chemical treatment.

  Examples of the energy ray irradiation treatment include corona discharge treatment, plasma treatment, electron beam irradiation treatment, ultraviolet ray irradiation treatment and the like. From the viewpoint of treatment efficiency, corona discharge treatment and plasma treatment are preferred, and corona discharge treatment is particularly preferred. Examples of the chemical treatment include a method of immersing in an aqueous oxidizing agent solution such as potassium dichromate solution or concentrated sulfuric acid and then thoroughly washing with water.

The coating liquid used in the present invention contains a sol-gel reactive silicon compound and hollow fine particles.
The sol-gel reaction is generally a method in which a sol composed of an alkoxide is converted into a gel that loses fluidity by hydrolysis and polycondensation reaction, and the gel is heated to obtain an oxide. The sol-gel reactive silicon compound is changed to a compound having a siloxane bond by the sol-gel reaction.
Examples of the sol-gel reactive silicon compound used in the present invention include one or more compounds selected from the group consisting of the following (a) to (c).
(A) Formula (1): A compound represented by SiX _n .
(B) At least one partially hydrolyzed polycondensation product of the compound represented by the formula (1).
(C) At least one fully hydrolyzed polycondensation product of the compound represented by the formula (1).

  In the compound represented by the formula (1) of the above (a), in the formula (1), X is a halogen atom such as a chlorine atom or a bromine atom; a monovalent hydrocarbon group which may have a substituent ; Oxygen atom; organic acid radical such as acetate radical and nitrate radical; β-diketonate group such as acetylacetonate; inorganic acid radical such as nitrate radical and sulfate radical; methoxy group, ethoxy group, n-propoxy group, n-butoxy group, etc. A hydrolyzable group such as an acetoxy group, propionyloxy group, trifluoroacetoxy group, benzoyloxy group or the like; a hydroxyl group; N represents the valence of the silicon.

As the compound represented by the formula (1),
Formula (2): R _a SiY _4-a
(In the formula, R represents a monovalent hydrocarbon group which may have a substituent, a represents an integer of 0 to 2, and when a is 2, R may be the same or different. Y represents a hydrolyzable group, and Y may be the same or different.)
A silicon compound represented by the formula is particularly preferred.

  Examples of the monovalent hydrocarbon group which may have a substituent include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group; a cyclopentyl group, A cycloalkyl group such as a cyclohexyl group; an aryl group optionally having a substituent such as a phenyl group, a 4-methylphenyl group, a 1-naphthyl group, or a 2-naphthyl group; an alkenyl group such as a vinyl group or an allyl group; Aralkyl groups such as benzyl group, phenethyl group and 3-phenylpropyl group; haloalkyl groups such as chloromethyl group, γ-chloropropyl group and 3,3,3-trifluoropropyl group; alkenyl groups such as γ-methacryloxypropyl group Carbonyloxyalkyl group; alkyl group having an epoxy group such as γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group; γ- It can be exemplified a perfluoroalkyl group such as trifluoromethyl group; an alkyl group having an amino group such as 3-aminopropyl group; an alkyl group having a mercapto group such as Le mercaptopropyl group. Among these, an alkyl group having 1 to 4 carbon atoms, a phenyl group, and a perfluoroalkyl group are preferable from the viewpoint of ease of synthesis and availability, and a perfluoroalkyl group is more preferable from the viewpoint of excellent antifouling properties.

  Y represents a hydrolyzable group. Here, the hydrolyzable group refers to a group that causes a siloxane bond.

Specific examples of the hydrolyzable group include alkoxy groups such as methoxy group, ethoxy group, cyclohexyloxy group, t-butyloxy group and propoxy group; acetoxy group, propionyloxy group, trifluoroacetoxy group, benzoyloxy group and the like. An acyloxy group; an oxime group (—O—N═C—R ′ (R ″)), an enoxy group (—O—C (R ′) = C (R ″) R ′ ″), an amino group, an aminoxy group ( -O-N (R ') R "), an amide group (-N (R')-C (= O) -R") and the like.
In these groups, R ′, R ″, and R ′ ″ each independently represent a hydrogen atom or a monovalent hydrocarbon group. Among these, Y is preferably an alkoxy group from the standpoint of availability. .

  The silicon compound represented by the formula (2) is preferably a silicon compound in which a is an integer of 0 to 2 in the formula (2). Specific examples thereof include alkoxysilanes, acetoxysilanes, oxime silanes, enoxysilanes, aminosilanes, aminoxysilanes, amidosilanes and the like. Among these, alkoxysilanes are more preferable because of their availability.

  In the formula (2), examples of the tetraalkoxysilane in which a is 0 include tetramethoxysilane and tetraethoxysilane. Examples of the organotrialkoxysilane in which a is 1 include methyltrimethoxysilane and methyltriethoxy. Examples include silane, methyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, and the like. Examples of the diorganodialkoxysilane in which a is 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane.

  The molecular weight of the compound represented by the formula (1) is not particularly limited, but is preferably 40 to 300, and more preferably 100 to 200.

  Further, at least one partial hydrolysis polycondensation product of the compound represented by the formula (1): the compound (b), and at least one complete hydrolysis polycondensation of the compound represented by the formula (1) Product: The compound (c) can be obtained by hydrolyzing at least one of the compounds represented by the formula (1) in whole or in part.

Compound (b) and compound (c) are, for example, silicon tetraalkoxides represented by Si (Or) ₄ (r represents a monovalent hydrocarbon group) in a molar ratio [H ₂ O] / [Or ] Is 1.0 or more, for example, 1.0 to 5.0, preferably 1.0 to 3.0, and can be obtained by hydrolysis in the presence of water.
Hydrolysis can be performed by stirring the whole volume at a temperature of 5 to 100 ° C. for 2 to 100 hours.

  When hydrolyzing the compound represented by the formula (1), an acid may be used as necessary. Although it does not specifically limit as an acid to be used, The obtained partial hydrolyzate and / or complete hydrolyzate are easy to become a two-dimensional crosslinked structure.

  The acid used is not particularly limited. For example, acetic acid, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluenesulfonic acid, oxalic acid, etc. Organic acids; inorganic acids such as hydrochloric acid, nitric acid, and halogenated silane; acidic sol-like fillers such as acidic colloidal silica and titania sol; These acids can be used alone or in combination of two or more.

  Instead of the acid, a base such as an aqueous solution of an alkali metal or alkaline earth metal hydroxide such as sodium hydroxide or calcium hydroxide, an aqueous ammonia, or an aqueous solution of amines may be used.

  The molecular weights of the compound (b) and the compound (c) are not particularly limited, but usually the weight average molecular weight is in the range of 200 to 5,000.

As the hollow fine particles used in the present invention, inorganic fine particles and organic compound hollow fine particles can be used without particular limitation. However, the hollow fine particles are preferably inorganic hollow fine particles in which cavities are formed inside the outer shell, and silica-based hollow fine particles. Can be used particularly preferably. Inorganic hollow fine particles include (A) a single layer of an inorganic oxide, (B) a single layer of a composite oxide composed of several types of inorganic oxides, and (C) a double layer of (A) and (B) above. Can be used.
The outer shell may be porous with pores, or the pores may be closed and the pores sealed against the outside of the outer shell. The outer shell is preferably a plurality of inorganic oxide coating layers comprising an inner first inorganic oxide coating layer and an outer second inorganic oxide coating layer. By providing the second inorganic oxide coating layer on the outer side, the fine pores of the outer shell are closed to make the outer shell dense, and furthermore, the inorganic hollow fine particles in which the inner pores are sealed can be obtained. In particular, when a fluorine-containing organic silicon compound is used for forming the second inorganic oxide coating layer, the refractive index is lowered, the dispersibility in an organic solvent is improved, and antifouling properties are further imparted. Examples of such fluorine-containing organic silicon compounds include 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, heptadecafluorodecylmethyldimethoxysilane, and heptadecafluorodecyl. Examples include trichlorosilane, heptadecafluorodecyltrimethoxysilane, trifluoropropyltrimethoxysilane, and tridecafluorooctyltrimethoxysilane.

  Although there is no restriction | limiting in particular in the average particle diameter of a hollow microparticle, It is preferable that it is 5-1,000 nm, It is more preferable that it is 10-500 nm, It is most preferable that it is 20-100 nm. If the average particle size is less than 5 nm, the effect of lowering the refractive index due to hollowness may be reduced. When the average particle diameter exceeds 1,000 nm, the transparency is extremely deteriorated and the contribution due to diffuse reflection may be increased. The average particle diameter can be determined as a number average particle diameter by observation with a transmission electron microscope. The weight ratio of the hollow fine particles to the silicon compound is preferably 85/15 to 30/70, more preferably 80/20 to 50/50. If the number of hollow fine particles is small, the refractive index does not decrease. Moreover, when there are too many hollow microparticles | fine-particles, hollow microparticles | fine-particles do not stick well and abrasion resistance deteriorates.

  The coating solution may further contain a known silane coupling agent. When a low refractive index layer is formed on a support using a coating liquid containing a silane coupling agent, the adhesion between the support and the low refractive index layer or / or other layers can be improved. .

The coating liquid may contain a binder resin. The binder resin is made of fluororesin, polyester resin, acrylic resin, urethane resin, vinyl chloride resin, epoxy resin, so as to meet conditions such as dispersibility of hollow fine particles, transparency of the porous body, and strength of the porous body. Melamine resin, fluororesin, silicone resin, butyral resin, phenol resin, vinyl acetate resin, UV curable resin, electron beam curable resin, emulsion resin, water-soluble resin, hydrophilic resin, mixture of these resins, and further Examples thereof include resins for coatings such as modified materials. Among these, a fluororesin, an acrylic resin, an epoxy resin, a urethane resin, and a silicone resin have good dispersibility of fine particles, and can be suitably used.

The coating solution containing the sol-gel reactive silicon compound and hollow fine particles used in the present invention contains a solvent in addition.
The solvent preferably includes water or a mixture of water and another organic solvent.
Examples of the organic solvent to be used include lower aliphatic alcohols such as methanol, ethanol, isopropanol (IPA), n-butanol and isobutanol; ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether and ethylene glycol monoethyl ether acetate And hydrophilic organic solvents such as diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; diacetone alcohol; and combinations of two or more thereof.

In combination with the hydrophilic organic solvent, aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as n-hexane and n-heptane; esters such as ethyl acetate and butyl acetate; methyl ethyl ketone and methyl Ketones such as isobutyl ketone; oximes such as methyl ethyl ketoxime; cell solves such as ethyl cellosolve and butyl cellosolve; and combinations of two or more of these can be used.
The content of the solvent in the coating solution is usually 80 to 99% by weight, preferably 90 to 99% by weight.

  The method for applying the coating solution onto a support containing a transparent resin is not particularly limited, and a known coating method can be employed. Examples of the coating method include a wire bar coating method, a dip method, a spray method, a spin coating method, a roll coating method, a die coating method, and a gravure coating method.

  The temperature at which the coating solution is applied onto a support comprising a transparent resin is usually 10 to 40 ° C, preferably 20 to 30 ° C, and the relative humidity is usually 10 to 80%, preferably 40-70%.

  A coating film can be obtained by applying the coating liquid on a support containing a transparent resin, and then the coating film can be dried to obtain a film on which the coating film has been formed. The drying temperature is preferably 20 to 130 ° C and the relative humidity is 0 to 80%. The drying temperature is 20 to 80 ° C and the relative humidity is 0 to 80% until the amount of the solvent remaining in the coating film is 5%. It is preferable to dry under the conditions of 80 to 130 ° C. and relative humidity of 0 to 20% when the amount of the solvent remaining in the coating film is less than 5%.

  The coating film (hereinafter referred to as a low refractive index layer) on the support obtained by the above method has a refractive index of preferably 1.38 or less. More preferred is 1.37 to 1.25, and particularly preferred is 1.36 to 1.32. The low refractive index layer obtained in the present invention provides a liquid crystal display device excellent in balance between visibility, scratch resistance and strength. The thickness of the low refractive index layer is preferably 10 to 1,000 nm, and more preferably 30 to 500 nm.

In the production method of the present invention, the film on which the coating is formed is irradiated with electromagnetic waves. Examples of electromagnetic waves include radio waves, infrared rays, visible rays, ultraviolet rays, X-rays, and γ (gamma) rays. Of these, ultraviolet rays are particularly preferred. By irradiating with electromagnetic waves, the surface hardness of the coating is increased and the scratch resistance is further improved.
The integrated irradiation amount of electromagnetic waves is preferably 50 to 500 mJ / cm ² , more preferably 100 to 450 mJ / cm ² , and still more preferably 200 to 400 mJ / cm ² .
When it is less than 50 mJ / cm ² , scratch resistance and pencil hardness do not increase. Moreover, when it exceeds 500 mJ / cm < ² >, a laminated film and a low refractive index layer will deteriorate and it will become weak.

In the present invention, it is preferable to provide other layers such as a primer layer and a high refractive index layer between the support containing the transparent resin and the low refractive index layer. In particular, by providing a high refractive index layer between a support containing a transparent resin and a low refractive index layer, a laminated film having excellent antireflection properties can be obtained.
The primer layer is formed for the purpose of imparting and improving adhesion between the support containing the transparent resin and other layers. Examples of the material constituting the primer layer include polyester urethane resins, polyether urethane resins, polyisocyanate resins, polyolefin resins, resins having a hydrocarbon skeleton in the main chain, polyamide resins, acrylic resins, and polyester resins. Examples thereof include resins, vinyl chloride / vinyl acetate copolymers, chlorinated rubber, cyclized rubber, and modified products obtained by introducing polar groups into these polymers. Among these, a modified product of a resin having a hydrocarbon skeleton in the main chain and a modified product of a cyclized rubber can be suitably used.

  Examples of the resin having a hydrocarbon skeleton in the main chain include a polybutadiene skeleton or a resin having a polybutadiene skeleton hydrogenated to at least a part thereof, specifically, polybutadiene resin, hydrogenated polybutadiene resin, styrene / butadiene / styrene. Examples thereof include block copolymers (SBS copolymers), hydrogenated products of styrene / butadiene / styrene block copolymers (SEBS copolymers), and the like. Among these, a modified product of a hydrogenated product of a styrene / butadiene / styrene block copolymer can be suitably used.

  As a compound for introducing a polar group used for obtaining a modified product of a polymer, a carboxylic acid or a derivative thereof is preferable. For example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and fumaric acid; halides, amides, imides, anhydrides and esters of unsaturated carboxylic acids such as maleyl chloride, maleimide, maleic anhydride and citraconic anhydride And the like; and the like. Among these, a modified product with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride is excellent in improving adhesion, and thus can be suitably used. Among the unsaturated carboxylic acids or anhydrides thereof, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are more preferable, and maleic acid and maleic anhydride are particularly preferable. These unsaturated carboxylic acids and the like can be modified by mixing two or more kinds.

  The method for forming the primer layer is not particularly limited, and examples thereof include a method in which a primer layer forming coating solution is formed on a support by a known coating method. The thickness of the primer layer is not particularly limited, but is usually 0.01 to 5 μm, preferably 0.1 to 2 μm.

The high refractive index layer is a layer having a refractive index larger than the refractive index of the support containing the transparent resin and the low refractive index layer.
The material constituting the high refractive index layer preferably contains a thermosetting resin or an active energy ray curable resin from the viewpoint of excellent transparency and mechanical strength. It is more preferable to contain.

Examples of the thermosetting resin include phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea co-condensation resin, silicone resin, poly Examples thereof include siloxane resins. Among these, melamine resins, epoxy resins, silicone resins, and polysiloxane resins are preferable from the viewpoint of excellent surface hardness, resistance to repeated fatigue, and scratch resistance.
Further, these resins can be used by adding a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier and the like, if necessary.

  The active energy ray-curable resin is a resin obtained by curing a prepolymer, an oligomer and / or a monomer having a polymerizable unsaturated bond or an epoxy group in a molecule by irradiation with energy rays. An active energy ray refers to an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or crosslinking molecules, and usually an ultraviolet ray or an electron beam is used.

  Examples of prepolymers and oligomers having a polymerizable unsaturated bond or epoxy group in the molecule include unsaturated polyesters such as unsaturated dicarboxylic acid and polyhydric alcohol condensates; methacrylates such as polyester methacrylate and polyether methacrylate , Acrylates such as polyester acrylate, epoxy acrylate and urethane acrylate, or cationic polymerization type epoxy compounds.

  Examples of the monomer having a polymerizable unsaturated bond or an epoxy group in the molecule include styrene monomers such as styrene and α-methylstyrene; acrylic acid such as methyl acrylate, ethyl acrylate, and acrylic acid-2-ethylhexyl. Esters; Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate; acrylic acid-2- (N, N-diethylamino) ethyl, acrylic acid-2- (N, N-dimethylamino) ethyl, etc. Unsaturated substituted amino alcohol esters of the above; unsaturated carboxylic acid amides such as acrylamide and methacrylamide; ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, tri Methylol Pro Polyfunctional acrylates such as polytriacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate; two in the molecule such as trimethylolpropane trithioglycolate and trimethylolpropane trithiopropylate Polythiols having the above thiol group; monomers having an epoxy group such as epoxy glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3,4-epoxycyclohexyl (meth) acrylate; and the like. In the present invention, prepolymers, oligomers and / or monomers having a polymerizable unsaturated bond or an epoxy group in these molecules can be used singly or in combination of two or more.

  In the present invention, the high refractive index layer preferably contains conductive fine particles in addition to the active energy ray-curable resin or thermosetting resin. By containing conductive fine particles in an active energy ray curable resin or a thermosetting resin, a high refractive index layer having a function as an antistatic film and at the same time excellent in mechanical strength can be formed.

  The conductive fine particles are not particularly limited as long as they are conductive fine particles, but metal oxide fine particles are preferable because of excellent transparency.

  Examples of the conductive metal oxide include antimony pentoxide, tin oxide doped with phosphorus (PTO), tin oxide, indium oxide doped with tin (ITO), and tin oxide doped with antimony (ATO). Indium oxide doped with zinc (IZO), zinc oxide doped with aluminum (AZO), tin oxide doped with fluorine (FTO), zinc oxide / aluminum oxide, zinc antimonate and the like. These metal oxide fine particles can be used singly or in combination of two or more. Among these, tin oxide doped with antimony pentoxide and / or phosphorus is preferable because of its excellent transparency.

  In the present invention, fine particles obtained by coating a conductive metal oxide on fine metal oxide fine particles having no conductivity as conductive fine metal oxide particles can also be used. For example, the surface of fine particles of titanium oxide, zirconium oxide, cerium oxide or the like having a high refractive index but no conductivity is coated with the conductive metal oxide to impart conductivity.

  The average particle diameter of the conductive fine particles is usually 200 nm or less, preferably 50 nm or less so as not to lower the transparency of the high refractive index layer. When it is larger than 200 nm, haze (turbidity) tends to increase. The particle size is measured by visual observation from a secondary electron emission image photograph obtained by a scanning electron microscope (SEM) or the like, or by a particle size distribution meter using a dynamic light scattering method, a static light scattering method, or the like. be able to.

  The high refractive index layer comprising the conductive fine particles and the active energy ray curable resin or the thermosetting resin is, for example, a high refractive index containing the conductive fine particles, the prepolymer, the oligomer and / or the monomer, and an appropriate solvent. The coating liquid for forming the rate layer is applied onto a support containing a transparent resin or other layer formed on the surface of the support, and the resulting coating film is cured with active energy rays. When it contains a mold resin, it can be formed by irradiating active energy rays, and when it contains a thermosetting resin, it can be formed by heating.

  The coating liquid for forming the high refractive index layer includes the conductive fine particles and a prepolymer, an oligomer and / or a monomer having a polymerizable unsaturated bond or an epoxy group in the molecule as an appropriate organic solvent. It can be prepared by dissolving or dispersing in.

  Examples of the organic solvent to be used include alcohols such as methanol, ethanol and isopropanol; glycols such as ethylene glycol and ethylene glycol monobutyl ether; aromatic hydrocarbons such as toluene and xylene; n-hexane, n-heptane and the like Aliphatic hydrocarbons; esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; oximes such as methyl ethyl ketoxime; cell solves such as ethyl cellosolve and butyl cellosolve; Combinations comprising the above;

  The content of the prepolymer, oligomer and / or monomer in the coating liquid for forming the high refractive index layer is not particularly limited, but since excellent coating suitability is obtained, the prepolymer, oligomer and / or Those containing 5% to 95% by weight of monomers are preferred.

  The content of the conductive fine particles in the coating liquid for forming the high refractive index layer is not particularly limited, but is preferably 30% by volume or more, more preferably 40% by volume to the total solid content of the high refractive index layer. 70% by volume. When the blending amount of the conductive fine particles is less than 30% by volume, the antistatic property of the obtained laminated film becomes poor.

  Moreover, when hardening of the coating liquid for forming a high refractive index layer is performed by ultraviolet irradiation, an ultraviolet polymerization initiator is added to the composition. UV polymerization initiators include radical polymerization initiators such as acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether; aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metathelone compounds, benzoin sulfonic acids Cationic polymerizable initiators such as esters; These can be used individually by 1 type or in combination of 2 or more types. The addition amount of the ultraviolet polymerization initiator is usually 0.1 with respect to 100 parts by weight of the prepolymer, oligomer and / or monomer having a polymerizable unsaturated bond or epoxy group in the molecule for forming the high refractive index layer. -10 parts by weight. Further, n-butylamine, triethylamine, tri-n-butylphosphine and the like can be mixed and used as a photosensitizer in the composition.

  A leveling agent and a dispersing agent can be appropriately added to the coating liquid for forming the high refractive index layer for the purpose of improving the uniformity and adhesion of the coating film. Examples of the leveling agent to be used include compounds that lower the surface tension such as silicone oil, fluorinated polyolefin, and polyacrylic ester, and examples of the dispersing agent include surfactants and silane coupling agents.

  For the purpose of imparting antiglare properties, particles that impart antiglare properties may be added to the coating liquid for forming the high refractive index layer. The particles imparting antiglare properties are not particularly limited as long as irregularities are formed on the surface of the high refractive index layer. In addition, the average particle diameter of the particles is preferably 0.5 to 10 μm and more preferably 1 to 7 μm in order to effectively form unevenness on the surface of the high refractive index layer.

Materials that make up the particles that impart antiglare properties include polymethyl methacrylate resin, fluorine resin, vinylidene fluoride resin, silicone resin, epoxy resin, nylon resin, polystyrene resin, phenol resin, polyurethane resin, crosslinked acrylic resin, and crosslinked resin Resin particles such as polystyrene resin, melamine resin, benzoguanamine resin, or TiO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ZrO ₂ , ITO, MgF ₂ , SiO ₂ , aluminosilicate Inorganic particles such as

  The method for applying the coating liquid for forming the high refractive index layer directly or via another layer on the support containing the transparent resin is not particularly limited, and a known coating method can be adopted. . Examples of the coating method include wire bar coating, dipping, spraying, spin coating, roll coating, gravure coating, and die coating.

  After apply | coating the coating liquid for forming a high refractive index layer on the support body containing transparent resin, it dries and obtains a film. When the film contains a thermosetting resin, it is cured by heating, and when it contains an active energy ray curable resin, it is cured by irradiation with an active energy ray to form a high refractive index layer. can do.

  The heating temperature and heating time, the irradiation intensity of the active energy ray and the irradiation time are not particularly limited, and can be appropriately set according to the composition of the material constituting the high refractive index layer to be used.

The thickness of the high refractive index layer is usually 0.5 to 30 μm, preferably 1 to 10 μm. If the thickness of the high refractive index layer is less than 0.5 μm, the hardness and mechanical strength of the layer may be lowered. On the other hand, if the thickness is greater than 30 μm, thickness unevenness may occur when coating.
The refractive index of the high refractive index layer is preferably 1.55 or more, more preferably 1.60 or more. The refractive index can be obtained by measuring using a known spectroscopic ellipsometer, for example.

  In the present invention, the high refractive index layer preferably exhibits a hardness of “HB” or higher in a pencil hardness test (test plate is a glass plate) shown in JIS K5600-5-4. When the pencil hardness of the high refractive index layer is in the above range, the high refractive index layer can also serve as the hard coat layer, and the member can be thinned.

In the present invention, when the high refractive index layer contains conductive fine particles, it has antistatic performance. The surface resistance value of the high refractive index layer having antistatic performance is preferably 1.0 × 10 ¹⁰ Ω / □ or less, more preferably 5.0 × 10 ⁹ Ω / □ or less.
The surface resistance value can be measured using a resistivity meter.

In the present invention, another layer may be provided on the low refractive index layer. Examples of the other layer include an antifouling layer. The antifouling layer is provided for protecting the low refractive index layer and enhancing the antifouling performance.
The material for forming the antifouling layer is not particularly limited as long as the function of the low refractive index layer is not inhibited and the required performance as the antifouling layer is satisfied. Usually, a compound having a hydrophobic group can be preferably used.
As specific examples, a perfluoroalkylsilane compound, a perfluoropolyethersilane compound, or a fluorine-containing silicone compound can be used. As a method for forming the antifouling layer, for example, a physical vapor deposition method such as vapor deposition or sputtering; a chemical vapor deposition method; a wet coating method; or the like can be used depending on the material to be formed. The thickness of the antifouling layer is preferably 20 nm or less, and more preferably 1 to 10 nm.

The laminated film obtained by the present invention is excellent in antireflection properties. Specifically, the reflectance at an incident angle of 5 ° is 1.4% or less at a wavelength of 430 to 700 nm, and the minimum reflectance in the wavelength range is 0.9% or less. When the reflectance is in the above range, there is no glare on the surface due to the reflected light, and thus the display content is excellent in visibility. Furthermore, since the reflectance is small over a wide band, the color tone of the display content can be accurately reproduced without coloring the reflected light.
Moreover, the laminated film obtained by the present invention is excellent in scratch resistance. Specifically, the variation in transmittance after the steel wool test is within 20%, preferably within 10%. The change in the transmittance after the steel wool test is the rate of change in transmittance measured before and after the test of rubbing the surface of the laminated film 20 times with a load of 0.025 MPa applied to the steel wool (ΔT ), The transmittance before the steel wool test is T ^a , and the transmittance after the steel wool test is T ^b .
ΔT = (T ^a −T ^b ) / T ^a × 100
The smaller the ΔT, the better the scratch resistance.
The transmittance can be obtained, for example, by measuring the total light transmittance using a known turbidimeter and using this as the transmittance.

  Since the laminated film obtained by the present invention is excellent in adhesion, planarity, and scratch resistance in addition to the antireflection properties, it can be used as various optical elements. Among these, it is preferable to use as an antireflection protective film.

  Anti-reflection protective films generally reduce contrast and image reflection due to reflection of external light in image display devices such as liquid crystal display devices, plasma display panels, EL elements, cathode ray tube display devices, and optical devices such as touch panels. Used to prevent. These antireflection protective films are often provided as an antireflection protective film for optical members usually formed in the uppermost layer on the viewing side in each optical device. Among these, it is preferable to apply to the protective film of the polarizing plate in a liquid crystal display device especially.

The present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. Parts and% are based on weight unless otherwise specified.
Evaluation in this example was performed by the following method.
(1) Refractive index (low refractive index layer, high refractive index layer)
Measured using a high-speed spectroscopic ellipsometer (manufactured by JA Woollam, M-2000U) at a measurement wavelength of 245 to 1000 nm, incident angles of 55 °, 60 ° and 65 °, and calculated based on the measured values Was the refractive index.
(2) Reflectance A black vinyl tape (No. 21: manufactured by Nitto Denko Corporation) is pasted on the surface of the support on which the low refractive index layer or the like is not provided, and a spectrophotometer (manufactured by JASCO Corporation: “UV” Using a visible near infrared spectrophotometer V-570 "), the reflection spectrum was measured at an incident angle of 5 °, and the reflectance at a wavelength of 550 nm was determined.
(3) Total light transmittance, haze Based on JIS K7361-1997, it measured using Nippon Denshoku Industries Co., Ltd. "turbidimeter NDH-300A".
(4) Scratch resistance The surface of the laminated film (the surface on which the low refractive index layer is provided) is reciprocated 20 times in a state where a load of 0.025 MPa is applied to steel wool # 0000. Then, the surface of the film after 10 reciprocations was visually observed and evaluated according to the following criteria.
(Double-circle): A crack is not recognized at all.
○: Slight scratches are observed when carefully observed.
Δ: Scratches are observed when viewed apart.
X: Deep scratches are clearly recognized.
(5) Fluctuation of total light transmittance after steel wool test When T ^a is the total light transmittance before the steel wool test and T ^b is the total light transmittance after the steel wool test, it can be obtained by the following equation.
ΔT = (T ^a −T ^b ) / T ^a × 100
The smaller the ΔT, the better the scratch resistance.
(6) Adhesiveness A cross-cut tape peeling test is performed in accordance with JIS D0202-1998. Using an adhesive tape (product name: CT24, manufactured by Nichiban Co., Ltd.), pressing this with the belly of the finger and bringing it into close contact with the surface of the laminated film (the surface on which the low refractive index layer is provided), The film was pulled and peeled in the direction of 90 °. Judgment is represented by the number of squares that do not peel out of 100 squares. The case where peeling does not occur is 100/100, and the case where peeling completely occurs is represented as 0/100. The larger the number of cells that do not peel, the better the adhesion.
(7) Pencil hardness It measured with the load of 500g according to JIS-K5700.
(8) The end of the tearable film is held by hand and is torn by hand from the end of the film.
A: There is power to tear. It is strong.
○: It can be torn without applying force.
X: It tears easily. The film is brittle. A crack has occurred.

1) Support comprising a transparent resin Support 1: A film made of a norbornene polymer (Zeonor film ZF14-40, manufactured by Nippon Zeon Co., Ltd., thickness 40 μm).

Support 2: Polyethylene terephthalate (PET) film (Lumirror T60 # 38, manufactured by Toray Industries, Inc., thickness 38 μm).

Support 3: Triacetylcellulose (TAC) film (KC4UX2M, manufactured by Konica Minolta, thickness 40 μm).

2) Preparation of coating liquid for forming a high refractive index layer (coating liquid for forming a high refractive index layer) Hexafunctional urethane acrylate oligomer (trade name: NK Oligo U-6HA, manufactured by Shin-Nakamura Chemical Co., Ltd.) 30 parts , 40 parts of butyl acrylate, 30 parts of isobornyl methacrylate (trade name: NK Ester IB, manufactured by Shin-Nakamura Chemical Co., Ltd.) and 10 parts of 2,2-diphenylethane-1-one were mixed with a homogenizer, and UV curable. A coating solution comprising the composition was prepared.
A 40% MIBK (methyl isobutyl ketone) solution of antimony pentoxide fine particles (average particle diameter 20 nm: hydroxyl groups are bonded to the antimony atoms appearing on the surface of the pyrochlore structure at a ratio of 1) to the coating solution. Then, the weight of the antimony pentoxide fine particles was mixed at a ratio of 50% by weight of the total solid content of the coating solution for forming a high refractive index layer to prepare a coating solution for forming a high refractive index layer.

3) Preparation of coating liquid (low refractive index layer forming coating liquid) for forming a low refractive index layer (1) Preparation of low refractive index layer forming coating liquid-1 Methanol was added to 208 parts of tetraethoxysilane. 356 parts are added, and 18 parts of water and 18 parts of 0.01N hydrochloric acid aqueous solution (“H ₂ O” / “OR” = 0.5) are added, and this is mixed well using a disper to prepare a mixed solution. Obtained. This mixed solution was stirred in a thermostatic bath at 25 ° C. for 2 hours to adjust the weight average molecular weight to 850, thereby obtaining a silicone resin solution. Next, hollow silica IPA (isopropanol) dispersion sol (solid content 20% by weight, average primary particle diameter of about 35 nm, outer shell thickness of about 8 nm, manufactured by Catalyst Kasei Kogyo Co., Ltd.) was added to the silicone resin solution with hollow silica fine particles / silicone resin ( (Condensed compound equivalent) is added so that the weight ratio is 70/30 based on the solid content, and further diluted with methanol so that the total solid content becomes 1%, and the coating solution for forming a low refractive index layer-1 Was prepared.

(2) Preparation of coating solution-2 for forming low refractive index layer 412 parts of methanol was added to 152 parts of tetramethoxysilane, and further 18 parts of water and 18 parts of 0.01N hydrochloric acid (“H ₂ O” / “OR”). = 0.5), and this was mixed well using a disper. The mixture was stirred for 2 hours in a constant temperature bath at 25 ° C., and the weight average molecular weight was adjusted to 850 to obtain a silicone resin. Next, in this silicone resin solution, silica methanol sol (manufactured by Nissan Chemical Industries, Ltd., PMA-ST, average particle size 10-20 nm) / silicone resin (condensed compound equivalent) has a weight ratio of 80/20 based on solid content. And diluted with methanol so that the total solid content is 3%, to prepare a coating solution-2 for forming a low refractive index layer.

(2) Preparation of coating solution-3 for forming a low refractive index layer 4-((4- (N, N-di (ethoxycarbonylmethyl) amino) phenyl) was added to the coating solution-1 for forming a low refractive index layer. Nine parts of -2,6-bis-trichloromethyl-S-triazine was added to prepare a coating solution-3 for forming a low refractive index layer.

(Example 1) Manufacture of laminated film A Corona discharge is performed on one side of the support 1 using a high-frequency transmitter corona discharge treatment apparatus (AGI-024 manufactured by Kasuga Denki Co., Ltd.) so that the surface tension is 0.072 N / m. Processed. A coating solution for forming a high refractive index layer is applied onto this using a die coater, dried at 100 ° C. for 2 minutes, irradiated with ultraviolet rays having an accumulated UV light amount of 1000 mJ / cm ² to cure the coating film and have a high refractive index. A laminated film having a layer thickness of 5 μm was obtained.
A corona discharge treatment was performed in the same manner as described above using a high-frequency transmitter corona discharge treatment apparatus (AGI-024 Kasuga Denki Co., Ltd.) again on the surface of the laminated film on which the high refractive index layer was laminated.

Next, the low refractive index layer-forming coating liquid-1 is applied to the surface of the laminated film on which the high refractive index layer is laminated and surface-treated with a die coater, and dried at 120 ° C. for 2 minutes. A laminated film having a thickness of 100 nm was obtained.
Finally, the laminated film was irradiated with ultraviolet rays so as to obtain a UV integrated light quantity of 400 mJ / cm ² to obtain a laminated film.

(Example 2)
A laminated film was obtained in the same manner as in Example 1 except that the support 2 was used instead of the support 1.

(Example 3)
A laminated film was obtained in the same manner as in Example 1 except that the support 3 was used instead of the support 1.

Example 4
A laminated film was obtained in the same manner as in Example 1 except that the coating liquid-3 for forming a low refractive index layer was used.

(Comparative Example 1)
A laminated film was obtained in the same manner as in Example 1 except that the film on which the low refractive index layer was laminated was not irradiated with ultraviolet rays.

(Comparative Example 2)
A laminated film was obtained in the same manner as in Example 2 except that the film on which the low refractive index layer was laminated was not irradiated with ultraviolet rays.

(Comparative Example 3)
A laminated film was obtained in the same manner as in Example 3 except that the film on which the low refractive index layer was laminated was not irradiated with ultraviolet rays.

(Comparative Example 4)
A laminated film was obtained in the same manner as in Example 1 except that the low refractive index layer forming coating solution-2 was used.

  The above-mentioned evaluation was performed about the obtained laminated film. The evaluation results are shown in Table 1.

  From the results shown in Table 1, the laminated film obtained by the present invention, as shown in Examples 1 to 3, uses a coating liquid containing hollow fine particles, and the same support that is not irradiated with ultraviolet rays is irradiated with ultraviolet rays. Compared with the body, the reflectance is low, the transparency (total light transmittance) is excellent, the scratch resistance, the adhesion, and the surface hardness are high. Further, when Example 1 is compared with Comparative Example 4 in which only the ultraviolet ray irradiation is performed without containing the hollow fine particles, it can be seen that the reflectance is greatly increased and the adhesion is also lowered. About Example 4, although the chemical | medical agent which generate | occur | produces an acid by light is added to what was implemented in Example 1, it turns out that pencil hardness is high.

Claims (5)

  A film on which a coating is formed by applying a coating solution containing a sol-gel reactive silicon compound and hollow fine particles directly or via another layer onto a support containing a transparent resin and drying it. And then irradiating the film with electromagnetic waves.   The method for producing a laminated film according to claim 1, wherein a refractive index of the low refractive index layer is 1.38 or less.   The manufacturing method of the laminated | multilayer film of Claim 1 and 2 which provides a high refractive index layer between the said support body and a low refractive index layer.   The method for producing a laminated film according to claims 1 to 3, wherein the transparent resin comprises at least one resin selected from the group consisting of an alicyclic structure-containing polymer resin, a cellulose polymer resin, and a polyester polymer resin. . The optical element which has a laminated | multilayer film obtained by the manufacturing method in any one of Claims 1-4.